JP5606526B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition and a wind power generator gear filled with the lubricating oil composition.

  Various performances are required for grease lubricants, gear oils, hydraulic oils, etc., and in recent years, engine parts have been improved due to higher performance, higher output, and severer operating conditions of internal combustion engines and industrial machinery. High performance such as wear resistance, heat resistance, sludge resistance, lubricating oil consumption characteristics, and fuel efficiency has been required. In addition, while the use environment of the lubricating oil becomes severe, there is a tendency to extend the life from consideration of environmental problems, and for this reason, reduction in viscosity reduction due to shear stress due to gears during engine operation, that is, There is a need for improved shear stability of lubricating oils. On the other hand, in order to improve the energy conversion efficiency of the engine or ensure good lubricity of the engine in a cryogenic environment, the oil film is retained at a high temperature of the lubricating oil, and the fluidity is retained at a low temperature. Such temperature viscosity characteristics are regarded as important.

  Accordingly, greases for lubricating oil, gear oils, hydraulic oils and the like are required to have long life, that is, low evaporation and good temperature viscosity characteristics.

  In particular, in a wind power generator that has been attracting attention as renewable energy in recent years, a gear box for converting wind power into electric power is installed at a high place in order to enjoy more stable wind power. In addition, it is often installed not only inland but also at sea from the viewpoint of stable supply of wind power and wind direction. For this reason, maintenance of gears, that is, replacement of the lubricating oil is very difficult, and as a result, higher shear stability is required for the lubricating oil. Further, from the viewpoint of energy conversion efficiency from wind power to electric power, there is a demand for good lubricity at extremely low temperatures such as −40 ° C., that is, high fluidity in a low temperature environment of the lubricating oil.

  Furthermore, in the gear oil for wind power generators, high micropitching prevention performance is required. Micropitting is a fatigue process caused just before gear damage by cycles of excessive stress in the rolling elastohydrodynamic lubrication (EHL) region under high loads. In this high load state, peeling of small pieces from the gear tooth surface due to repeated compressive stress is referred to as micropitting, and the lubricating oil used for the gear oil for wind power generators is required to have high micropitting resistance.

  Various synthetic lubricating oils have been developed against the above background (Patent Documents 1, 2, etc.).

Special table 2008-542524 gazette Special table 2009-500489

  However, the lubricating oil compositions described in Patent Document 1 and Patent Document 2 have room for improvement, particularly in fields where high shear stability is required, such as gear oil for wind power generators.

  The problem to be solved by the present invention relates to a lubricating oil composition having high oxidation stability and heat resistance and excellent in high temperature viscosity characteristics, and a lubricating oil, and in particular, high shear stability and excellent An object of the present invention is to provide a lubricating oil composition having both low temperature viscosity characteristics and excellent micropitting resistance.

  As a result of intensive studies to solve the above problems, a specific lubricating base oil, a specific α-olefin having a specific number of carbon atoms is obtained by homopolymerization or copolymerization with another α-olefin, By blending a specific amount of low molecular weight polymer having a molecular weight distribution and a specific ester and including a specific amount of boron atom, extremely excellent shear stability, temperature viscosity characteristics, low temperature viscosity characteristics, micro resistance The present inventors have found that it exhibits pitching performance and have completed the present invention.

That is, the lubricating oil composition according to the present invention includes the following (i) to (iii), a kinematic viscosity at 40 ° C. of 30 mm ² / s to 750 mm ² / s and boron of 5 ppm to 75 ppm: A lubricating oil composition containing atoms.
(I) The kinematic viscosity at 100 ° C. of 90 to 10% by mass is 45 mm ² / s or less, 60 mol% or more of the structural unit is composed of 1-decene, and the acid value is less than 0.1 mgKOH / g (both ) Polymer (ii) The kinematic viscosity at 100 ° C. of 5 to 85% by mass is 35 mm ² / s to 1,500 mm ² / s and 90 mol% or more of the structural unit is composed of 1-octene, and the gel permeation (Co) polymer (iii) having a molecular weight distribution of 1.8 or less as measured by attraction chromatography, and a fatty acid ester having a kinematic viscosity at 100 ° C. of 5 to 15% by mass of 20 mm ² / s or less (provided that (i ) To (iii) is 100% by mass.)

  According to the present invention, a lubricating oil composition having excellent shear stability as compared with conventional lubricating oils and having both high temperature viscosity characteristics, excellent low temperature viscosity characteristics, and anti-micropitting performance can be obtained. In particular, a lubricating oil composition capable of maintaining the above characteristics even under high load conditions, also called extreme pressure lubrication conditions, can be obtained.

FIG. 1 is a view for explaining an example of the wind power generator of the present invention, showing a cross-sectional view partially cut in the length direction of the wind power generator, and partially showing the wind power generator from the front side. A perspective view visually observed is shown in FIG. FIG. 2 is an enlarged perspective view of the wind power generator shown in FIG. FIG. 3 is an enlarged perspective view of a portion Y of the wind turbine generator shown in FIG. 1 as viewed. FIG. 4 is a perspective view illustrating a drive strung module used for driving a wind turbine generator.

≪Lubricating oil composition≫
The lubricating oil composition of the present invention has a kinematic viscosity at 40 ° C. of 30 mm ² / s to 750 mm ² / s, more preferably a dynamic viscosity at 40 ° C. of 190 mm ² / s to 750 mm ² / s. If it is 750 mm < ² > / s or less, it will be excellent in fuel-saving performance and energy conversion efficiency. Further, if the kinematic viscosity at 40 ° C. is 30 mm ² / s or more, good lubrication characteristics are exhibited at high temperatures, and if it is 190 mm ² / s or more, good lubricity is exhibited as gear oil in a high load state. If the kinematic viscosity at 40 ° C. is in the above range, a sufficient oil film can be maintained even at a high temperature, so that the shear stability is more excellent.

  In the lubricating oil composition, the kinematic viscosity at 40 ° C. is the kinematic viscosity at 100 ° C. of (i) decene (co) polymer and (ii) octene (co) polymer described later, or (i) decene (co) It can be adjusted by appropriately changing the blending amount of the polymer)) and the polymer (ii) octene (co) polymer. For example, the blending ratio can be estimated by the method described in Appendix 1 of JIS K-2283 and adjusted based on this.

Further, the lubricating oil composition of the present invention has the following (i) (co) polymer comprising 1-decene having a kinematic viscosity at 100 ° C. of 45 mm ² / s or less, and (ii) a kinematic viscosity at 100 ° C. of 35 mm. ^And a (co) polymer composed of 1-octene that is ² / s or more and 1,500 mm ² / s or less. In the present specification, “(co) polymer” includes both a homopolymer and a copolymer.

  The (co) polymer composed of 1-decene and the (co) polymer composed of 1-octene are preferably 80% by mass or more in the lubricating oil composition of the present invention. If it exists in this range, it has high oxidation stability and heat resistance.

In the present invention, (i) a (co) polymer comprising 1-decene having a kinematic viscosity at 100 ° C. of 45 mm ² / s or less is industrially known as a poly-α-olefin (PAO). It is generally used as a base oil for lubricating oil. Such (co) polymers composed of 1-decene are sold under trademarks such as NEXBASE (manufactured by NESTE OIL), SPECTRASYN (manufactured by EXXONMOBIL CHEMICAL), DURASYN (manufactured by INEOS), and are readily available. Is possible. This (co) polymer is a homopolymer of 1-decene or a copolymer of 1-decene and 1-octene and / or 1-dodecene, but at least 60 mol% or more of the structural unit is It consists of 1-decene. When it is a copolymer with 1-octene, the low-temperature viscosity characteristics may be lowered, and when it is a copolymer with 1-dodecene, shear stability may be lowered. Therefore, a homopolymer of 1-decene Are preferably used.

  Moreover, it is preferable that the (co) polymer consisting of (i) 1-decene has an acid value measured by JIS K2501 of less than 0.1 mgKOH / g. More preferably, it is less than 0.05 mgKOH / g. Within this range, the resulting lubricating oil composition has excellent oxidation stability and heat resistance.

(I) The kinematic viscosity at 100 ° C. of the (co) polymer composed of 1-decene is 45 mm ² / s or less, preferably 11 mm ² / s or less. When it is 11 mm ² / s or less, the low-temperature viscosity characteristics of the lubricating oil composition are more excellent.

  (I) The (co) polymer comprising 1-decene may be used alone or in combination of two or more.

The 1-decene (co) polymer can be produced by a conventionally known method. For example, using a catalyst such as BF ₃ or AlCl ₃ , a (co) polymer having a desired molecular weight can be obtained by adjusting the polymerization temperature and polymerization time. The kinematic viscosity at 100 ° C. can be adjusted by this molecular weight adjustment (that is, the high viscosity is high and the low viscosity is low). Moreover, in order to adjust an acid value to less than 0.1 mgKOH / g, the method of passing through a hydrogenation process by the well-known method about the obtained (co) polymer is common. The production methods of these 1-decene (co) polymers are described in US Pat. Nos. 3,149,178, 3,382,291, 3,742,082, 3,780,128, 4,172,855. And patents such as 4,956,122.

(Ii) A (co) polymer having a kinematic viscosity at 100 ° C. of 35 mm ² / s or more and 1,500 mm ² / s or less has a carbon atom number of 8, that is, a (co) polymer polymerized using 1-octene as a monomer. The content of the structural unit is 90 to 100 mol%, preferably 95 to 100 mol%. In other words, this (co) polymer is a homopolymer of 1-octene or a copolymer with other monomers. If it exists in this range, the property of the lubricating oil composition in this invention will become substantially equivalent to the lubricating oil composition containing the polymer which homopolymerized 1-octene. In the lubricating oil composition, by combining such (ii) octene (co) polymer with (i) decene (co) polymer, shear stability and low temperature viscosity characteristics can be improved, and oxidation stability, Heat resistance and temperature viscosity characteristics can also be improved. In order to further improve the shear stability and low temperature viscosity characteristics of the lubricating oil composition, it is preferable to use a homopolymer of 1-octene together with (i) a decene (co) polymer.

  The monomer mainly constituting the (co) polymer in (ii) is 1-octene. When the number of carbon atoms is 6, that is, 1-hexene, the temperature viscosity characteristics and the low temperature viscosity characteristics may be significantly deteriorated. Further, when the number of carbon atoms is 10, that is, 1-decene, the shear stability of the lubricating oil composition may be significantly lowered.

  The shear stability is evaluated by a KRL shear stability test in accordance with the method described in German Industrial Standard DIN 52350-6. The lubricating oil composition was placed under shearing conditions (1450 rpm) at 60 ° C. for 20 hours, and the kinematic viscosity decrease rate at 40 ° C. after the test was evaluated with respect to the kinematic viscosity at 40 ° C. before the test. The shear stability is better.

  Further, 1-octene as a raw material can be obtained at a lower cost than 1-decene. Therefore, the amount of 1-decene used in the lubricating oil composition according to the present invention is relatively reduced compared to the synthetic lubricating oil composition described in Patent Document 1 or Patent Document 2 obtained by the prior art. Therefore, it also has an advantage that it can be manufactured at low cost industrially.

  The structural unit other than 1-octene constituting the (co) polymer in (ii) is preferably an α-olefin having 2 to 14 carbon atoms (excluding 1-octene), and the inclusion of these structural units. The rate is in the range of 0-10 mol%, preferably in the range of 0-5 mol%. If the α-olefin is selected from the above and / or the content of the α-olefin is described above, the oxidation stability, heat resistance and low temperature viscosity characteristics of the lubricating oil composition are excellent.

The kinematic viscosity at 100 ° C. of the (co) polymer comprising 1-octene in the present invention is 35 mm ² / s or more and 1,500 mm ² / s or less. Preferably, it is 150 mm ² / s or more and 1,200 mm ² / s or less, and if it is 150 mm ² / s or more, in the case of gear oil, industrial lubricating oil, wind generator gear oil or bearing lubricating oil, Since the content of the (co) polymer composed of 1-octene having a high viscosity is relatively reduced with respect to the (co) polymer composed of 1-decene which is oil, the low temperature viscosity characteristics are excellent. If it is 1,200 mm ² / s or less, the shear stability is more excellent.

  The number average molecular weight can be measured by gel permeation chromatography (GPC) calibrated using a standard substance (monodispersed polystyrene (PSt)) having a known molecular weight, but 1-octene in the present invention is used as a monomer. The number average molecular weight (Mn) of the (co) polymer is preferably in the range of 500 to 15,000, more preferably in the range of 3,000 to 12,000. When the number average molecular weight is within this range, the resulting lubricating oil composition has an excellent balance between low-temperature viscosity characteristics and shear stability.

  Further, the molecular weight distribution (Mw / Mn) of the (co) polymer comprising 1-octene in the present invention is in the range of 1.8, preferably in the range of 1.1 to 1.8, more preferably 1. In the range of 2 to 1.7. If it exists in this range, the shear stability of the lubricating oil composition obtained will be excellent.

  (Ii) The (co) polymer comprising octene may be used alone or in combination of two or more.

(Production of (co) polymer comprising (ii) octene in the present invention)
In the production of the (co) polymer comprising 1-octene as described above, JP-A-2-41303, JP-A-2-41305, JP-A-2-274703, JP-A-2-274704 No. 3, JP-A-3-179905, JP-A-3-179006, JP-A-3-19396, JP-A-4-69394, JP-A-5-17589, JP-A-6-122718. JP-A-8-120127, JP-A-8-239414, JP-A-10-087716, JP-A-2000-212194 or WO01 / 27124, WO02 / 074855, WO04 / 029062, EP0881236, EP1416000. Referring to the catalyst used in the production of α-olefin (co) polymer It can be produced by Rukoto.

Specifically, in the production of a (co) polymer having 1-octene as a monomer, for example, a transition metal compound (such as a transition metal compound of Group 4 of the periodic table) (A),
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum compound,
(B-3) an organoaluminum oxy compound, and (B-4) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair,
A homopolymer by homopolymerizing 1-octene in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of 1-octene and the above-mentioned other monomers. Alternatively, a copolymer can be obtained.

More specifically, the transition metal compound (A) and the compound (B) are as follows.
[(A) Transition metal compound]
The transition metal compound (A) used in the present invention can be used without particular limitation as long as it is a transition metal compound of the Periodic Tables IV to VI having a known olefin polymerization ability. Examples thereof include transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds, and the like. Preferred are group IV transition metal halides, more preferably group IVB transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds, and the like. Hereinafter, preferred forms of these transition metal compounds (A) will be described.

  Specific examples of transition metal halides, transition metal alkylates, and transition metal alkoxylates include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium.

  Examples of the non-crosslinkable or crosslinkable metallocene compound include compounds represented by the following general formula (1) as a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton.

ML _x (1)
In the formula, M represents one transition metal atom selected from Group IV of the Periodic Table, and is preferably zirconium, titanium, or hafnium, which is a Group IVB transition metal. x is the valence of the transition metal and represents the number of L. L represents a ligand or group coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral atom having 10 or less carbon atoms, a neutral configuration capable of coordinating with a conjugated or nonconjugated diene, an anionic ligand or a lone electron pair. One group or atom selected from the ligand in the same or different combination.

  Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an alkyl-substituted cyclopentadienyl group, an indenyl group, an alkyl-substituted indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. Groups, alkyl-substituted fluorenyl groups, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the general formula (1) includes two or more ligands having a cyclopentadienyl skeleton, among the ligands having two cyclopentadienyl skeletons, an alkylene group, It may be bonded via a substituted alkylene group, a silylene group, a substituted silylene group or the like. (In the following description, such a compound may be referred to as a “crosslinkable metallocene compound”. Other than such a compound may be referred to as a “non-crosslinkable metallocene compound”.)
Of these, preferred are compounds represented by the following general formula (2).

ML _a X _b (2)
(In the formula, M represents one type of transition metal atom selected from Group IV of the periodic table, preferably zirconium, titanium, or hafnium, which is a transition metal of Group IVB, and L represents a configuration coordinated to the transition metal. A ligand, a is an integer of 1 or more and represents the number of L, X is a halogen bonded to a transition metal, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon number of 10 or less One or more groups or atoms selected from neutral, conjugated or non-conjugated dienes, anionic ligands or neutral ligands capable of coordinating with lone pairs, in the same or different combinations, and b is 1 or more (It is an integer and indicates the number of X.)
In the general formula (2), L is a ligand coordinated to a transition metal, and at least one of them is a ligand having a cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl And an alkyl-substituted cyclopentadienyl group such as a hexylcyclopentadienyl group; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; a fluorenyl group, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

  In the said General formula (2), a is an integer greater than or equal to 1, and shows the number of L.

  In the general formula (2), M is zirconium, titanium, or hafnium.

X is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone electron pair bonded to a transition metal. A group or atom selected from the same or different combinations of potential neutral ligands. Specific examples of halogen include fluorine, chlorine, bromine and iodine. Specific examples of hydrocarbon groups Is methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1 , 2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-thio Rohekishiru, and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations.

  In the said General formula (2), b is an integer greater than or equal to 1, and shows the number of X.

  When the compound represented by the general formula (2) includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons include ethylene, propylene and the like A substituted alkylene group such as diphenylmethylene; an alkylidene group such as isopropylidene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. Further, the ligands having two or more cyclopentadienyl skeletons may be the same or different.

  When the compound represented by the general formula (2) is a ligand having two cyclopentadienyl skeletons, it is more specifically represented by the following general formula (3) or (4).

(In the formula, M represents one transition metal atom selected from group IV of the periodic table, preferably zirconium, titanium or hafnium, which is a group IVB transition metal, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are selected from hydrogen, hydrocarbon group, and silicon-containing hydrocarbon group, and may be the same or different from R ¹ to R ¹⁰ The adjacent substituents may be bonded to each other to form a ring, and X is a halogen, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, neutral, conjugated or non-carbon having 10 or less carbon atoms. One group or atom selected from the same or different combinations from conjugated dienes, anionic ligands, or neutral ligands capable of coordinating with lone pairs, n is 1 or 2, and the number of X Is shown.)

(In the formula, M represents one transition metal atom selected from group IV of the periodic table, preferably zirconium, titanium or hafnium, which is a group IVB transition metal, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, hydrocarbon group and silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R ¹ to R ⁸ are They may be bonded to each other to form a ring, and X is a halogen, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, anion coordination A group or atom selected from the same or different combinations from neutral ligands capable of coordinating with a lone pair or a lone electron pair, n is 1 or 2, and indicates the number of X, Q is , Carbon, silicon or germanium, Y ¹ and Y ² are hydrogen , Hydrocarbon groups and silicon-containing hydrocarbon groups, which may be the same or different, and may be bonded to each other to form a ring.)
In the general formula (3) or (4), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. These are alkylaryl groups of several 7 to 20, and may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, and 1-ethyl-1-methylpropyl. 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1- Cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.

  In the general formula (3) or (4), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, and tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the general formula (3) are hydrogen, hydrocarbon group, silicon-containing carbon They are selected from hydrogen groups and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above. In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and are the same. But it can be different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ¹⁰ on the cyclopentadienyl ring of the general formula (3) may be bonded to each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like. Moreover, the adjacent substituents from R ¹ to R ⁸ on the cyclopentadienyl ring of the general formula (4) may be bonded to each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

  In the present invention, M in the general formula (3) or (4) represents one kind of transition metal atom selected from Group IV of the periodic table, and is preferably a transition metal of Group IVB, zirconium, titanium or hafnium.

X is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral atom having 10 or less carbon atoms, a neutral configuration capable of coordinating with a conjugated or nonconjugated diene, an anionic ligand or a lone electron pair. A group or atom selected from the same or different combinations from the ligand; specific examples of the halogen are fluorine, chlorine, bromine and iodine; specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetra Methylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, etc. That. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations.

  n is 1 or 2, and indicates the number of X.

  Specific examples of the general formula (3) include cyclopentadienyl trichloride, cyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (penta Methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Bis (butylcyclopentadienyl) zirconium including propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, etc. Bis (dimethylcyclopentadienyl) zirconium dichloride, including bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, etc. Bis (methylpropylcyclopentadienyl) containing diethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride, etc. ) Bis (methylbutylcyclopentadienyl) zirconium dichloride including zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, etc. Specific examples of the general formula (4) include ethylene bis (indenyl) zirconium dichloride, ethylene bis (1-indenyl) titanium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (di-tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium Dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzindenyl) zirconium dichlori Dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylethylenebis (2-methylindenyl) zirconium dichloride, dimethylethylene Bis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, isopropyl Liden (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (methyl-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, Isopropylidene (methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydridodibenz Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfullyl) Rhenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (methyl-tert-butylcyclopentadienyl) (Fluorenyl) zirconium dichloride, diphenylmethylene (methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (methyl-tert-butylcyclopentadienyl) ( Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexyl Down (cyclopentadienyl) (3,6-di -tert- butyl fluorenyl) zirconium dichloride, cyclohexylene (methylcyclopentadienyl) (fluorenyl) zirconium dichloride,

Cyclohexylene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (methyl-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (methyl-tert-butylcyclopentadienyl) ( 3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, di (p-tolyl) methylene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopente) Tadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert- Butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di ( p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert -Butylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methyle (Cyclopentadienyl) (fluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (pn-n- Butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorene Nyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7- Dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (Fluorenyl) zirconium dimethyl, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (cyclo Pentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, di (p-tert-butyl) Phenyl) methylene ( Clopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, Di (p-isopropylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclope Ntadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride cyclopentylidene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadi) Enyl) (2,7-ditert-butylfull Oleenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, monophenyl Methylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride , Diethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (Cyclopentadienyl ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (octamethylocta Hydrodibenzofluorenyl) Zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride , Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, die Rumethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadiene) Enyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride,
Adamantylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, dimethylmethylene ( Cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclo Pentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (octa Tiltetrahydrodicyclopentafluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, adamantyl Den (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium Dichloride, diphenylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) ) (Dibenzofluorenyl) Zirconium dichloride, diethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopenta Fluorenyl) Zirconium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (fluorenyl) Luconium dichloride, propylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Propylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (methyl) (p-tolyl) methylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) di Conium dichloride, (methyl) (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2 , 7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) ) Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (3,6-diter t-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (methyl) (benzyl) Examples include methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and the like.

  In addition to titanium compounds and hafnium compounds having the same three-dimensional structure, bromide, iodide, etc., for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, Examples thereof include transition metal compounds described in Kaihei 3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300787, WO01 / 27124A1, and the like. .

  The transition metal compound (A) used in the polymerization examples and comparative polymerization examples of the present invention is specifically represented by the following formula (6), but is not limited to this compound in the present invention. In addition, you may use the transition metal compound (A) represented by following formula (5), (7), (8)-(9).

  In the polymerization example of the present invention, compound (6) is described as (methyl) (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride.

  The structure of the obtained transition metal compound is determined by 270 MHz 1H-NMR (JEOL GSH-270) and FD-mass spectrometry (JEOL SX-102A).

  These transition metal compounds (A) may be used alone or in combination of two or more.

[(B-1) Organometallic compound]
(B-1) As the organometallic compound, specifically, an organometallic compound represented by the following formula (10) is used.

General formula R ^a R ^b M ³ (10)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.

  Moreover, these organometallic compounds (B-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

[(B-2) Organoaluminum compound]
Examples of the organoaluminum compound forming the olefin polymerization catalyst (B-2) include an organoaluminum compound represented by the following general formula (11), a group 1 metal represented by the following general formula (12), and aluminum. And a complex alkylated product thereof.

R ^a _m Al (OR ^b ) _n H _p X ² _q (11)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m represents 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

M ² AlR ^a ₄ (12)
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Alkylate complex of aluminum and aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the organoaluminum compound represented by the general formula (11) include compounds represented by the following general formula (13), (14), (15), or (16).

R ^a _m Al (OR ^b ) _3-m (13)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ A number of 3.)
R ^a _m AlX ² _3-m (14)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m is preferably 0 <m <3.)
R ^a _m AlH _3-m (15)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3.)
R ^a _m Al (OR ^b ) _n X ² _q (16)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m represents (0 <m ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3)
More specifically, examples of the aluminum compound represented by the general formula (13), (14), (15), or (16) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, Tri-n-alkylaluminums such as pentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri 3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-me Tri-branched alkylaluminums such as ruhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; diisopropylaluminum hydride, diisobutylaluminum formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z; dialkylaluminum hydrides such as hydride (wherein, x, y, z are each a positive number, and z ≦ 2x.) Alkenyl aluminum such as isoprenyl aluminum represented by isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide, etc. Alkyl aluminum alkoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide dialkylaluminum alkoxides such as Sid; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui blanking such butoxide alkyl sesquichloride alkoxide; general formula R ^a _2.5 Al (OR ^b) Partially alkoxylated alkylaluminum having an average composition such as _0.5 ; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6 -Di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl) Alkyl aluminum aryloxides such as til-4-methylphenoxide); dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, Alkyl aluminum sesquihalides such as ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkylaluminum Other partially hydrogenated alkylaluminums such as ethylaluminum dihydride, propylaluminum dihydride, etc .; partially alkoxy such as ethylaluminum ethoxychloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide And alkylated aluminum and the like.

A compound similar to the compound represented by the general formula (11) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound represented by the general formula (12) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

  Of these, organoaluminum compounds are preferred.

  The organoaluminum compound represented by the general formula (11) or the complex alkylated product of the Group 1 metal and aluminum represented by the general formula (12) is used singly or in combination of two or more. .

[(B-3) Organoaluminum oxy compound]
(B-3) The organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(I) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(II) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(III) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-2).

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The above organoaluminum compounds are used singly or in combination of two or more.

  The benzene-insoluble organoaluminum oxy-compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, Those which are insoluble or hardly soluble are preferred.

  Aluminoxane prepared from trimethylaluminum is called methylaluminoxane or MAO and is a particularly frequently used compound.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  Examples of the organoaluminum oxy compound include an organoaluminum oxy compound containing boron represented by the following general formula (17).

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
The organoaluminum oxy compound containing boron represented by the general formula (17) contains an alkyl boronic acid represented by the following general formula (18) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. Thus, it can be produced by reacting at -80 ° C to room temperature for 1 minute to 24 hours.

R ^c B (OH) ₂ (18)
(In the formula, R ^c represents the same group as described above.)
Specific examples of the alkyl boronic acid represented by the general formula (18) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the general formula (11) or (12). .

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  These organoaluminum oxy compounds (B-3) are used singly or in combination of two or more.

[(B-4) Compound that reacts with the Group IV transition metal compound (A) to form an ion pair]
Examples of the compound (B-4) that forms an ion pair by reacting with the aforementioned group IV transition metal compound (A) include JP-A-1-501950, JP-A-1-502020, and JP-A-3-179005. Lewis acids, ionic compounds, borane compounds, carborane compounds and the like described in JP-A No. 3-179006, JP-A 3-207703, JP-A 3-207704, USP-5321106, etc. Can be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, trimethylboron, triisobutylboron and the like can be mentioned.

  Examples of the ionic compound include a compound represented by the following general formula (19).

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^e , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl). And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

  Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4 -Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) volley Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o -Tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadeci Examples include rumethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecylmethylammonium and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate and the like. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

  Further, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, or the following formula (20) or (21) And a borate compound containing an active hydrogen represented by the following formula (22), a borate compound containing a silyl group represented by the following formula (23), and the like.

(In the formula, Et represents an ethyl group.)

[B-Qn (Gq (T -H) r) z] - A + (22)
In formula (22), B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Examples include naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bond radical G is an r + 1 bond, that is, one bond is bonded to a borate anion, and the other bond r of G is bonded to a (TH) group. A ⁺ is a cation.

T in the above formula (22) represents O, S, NR ^j , or PR ^j , and R ^j represents a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride. q is an integer of 1 or more, preferably 1. The TH group includes —OH, —SH, —NRH, or —PR ^j H, where R ^j is a hydrocarbyl radical or hydrogen having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. is there. Preferred R ^j groups are alkyl, cycloalkyl, allyl, allylalkyl or alkylallyl having 1 to 18 carbon atoms. -OH, -SH, -NR ^j H or -PR ^j H may be, for example, -C (O) -OH, -C (S) -SH-C (O) -NR j H, and C (O) - PR ^j H is also acceptable. The most preferred group having active hydrogen is the -OH group. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical and the like. Here, n + z is 4.

[B-Qn (Gq (TH) r) z] in the above formula (22) includes, for example, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) Borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris [3,5-di (trifluoromethyl) phenyl] (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxy Butyl) borate, tris ( Ntafluorophenyl) (4-hydroxycyclohexyl) borate, tris (pentafluorophenyl) [4- (4-hydroxyphenyl) phenyl] borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate, etc. Most preferred is tris (pentafluorophenyl) (4-hydroxyphenyl) borate. Furthermore, it is preferable to substitute the —OH group of the borate compound with —NHR ^j (where R ^j is methyl, ethyl, t-butyl).

Examples of A ⁺ that is a counter cation of the borate compound include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Also included are metal cations and organometallic cations whose confidence is easily reduced. Specific examples of these cations include triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tributylammonium, dimethylammonium, dipropylammonium, dicyclohexylammonium, trioctylammonium, N, N-dimethylammonium, diethylammonium, 2,4,6-pentamethylammonium, N, N-dimethylphenylammonium, di- (i-propyl) ammonium, dicyclohexylammonium, triphenylphosphonium, triphosphonium, tridimethylphenyl Phosphonium, tri (methylphenyl) phosphonium, triphenylphosphonium ion, triphenyloxonium On, triethyl oxonium ions, Piriniumu, silver ions, gold ions, platinum ions, copper ions, para indium-ion, mercury ion, and a ferrocenium ion. Of these, ammonium ions are particularly preferred.

[B-Qn (Gq (SiR k R l R m) r) z] - A + ... (23)
In formula (23), B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Examples include naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bond radical G is bonded to r + 1, that is, one bond is bonded to the borate anion, and the other bond r of G is bonded to the (SiR ^k R ^l R ^m ) group. A ⁺ is a cation. q is an integer of 1 or more, preferably 1.

R ^k , R ^l and R ^{m in the} above formula (24) represent a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, a hydrogen radical, an alkoxy radical, a hydroxy radical or a halogen compound radical. . R ^k , R ^l and R ^m may be the same or independent. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical, and more preferably a pentafluorobenzyl radical. Here, n + z is 4.

The formula (23) in the [B-Qn (Gq (SiR k R l R m) r) z] - as, for example, triphenyl (4-dimethylchlorosilyl phenyl) borate, diphenyl chromatography di (4-dimethylchlorosilyl phenyl ) Borate, triphenyl (4-dimethylmethoxysilylphenyl) borate, tri (p-tolyl) (4-triethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-dimethylchlorosilylphenyl) borate, tris (penta Fluorophenyl) (4-dimethylmethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-trimethoxysilylphenyl) borate, tris (pentafluorophenyl) (6-dimethylchlorosilyl-2-naphthyl) borate and the like. .

A ⁺ which is the counter cation of the borate compound is The same thing as A ^<+> in the said Formula (22) is mentioned.

  Specific examples of the borane compound include decaborane, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Anion salts such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.

  Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonarborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1 -Trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, Tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbundecaborate, tri (n- Butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Undecahydride-8-butyl-7,9-dicarbaoundeborate, tri (n-butyl) ) Ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium Salts of anions such as undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ) Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbau) Decaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride) -7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7 , 8-dicarboundeborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbounde Borate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (Undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV), etc. Examples thereof include salts of metal carborane anions.

  In addition, the compound (B-4) which reacts with the above Group 4 transition metal compound (A) to form an ion pair can be used in combination of two or more.

  As the component (B) used in the present invention, specifically, a commercially available MAO / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd. using the (A-3) organoaluminum oxy compound shown above is suitable. Used for.

  In addition, in the preparation of the olefin polymerization catalyst used in the present invention, a carrier can be used as necessary. The carrier is usually an inorganic or organic compound and is a granular or particulate solid. Among these, examples of the inorganic compound include porous oxides, inorganic chlorides, clays, clay minerals, and ion exchange layered compounds.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO _2- MgO or the like can be used.

  The octene (co) polymer (ii) is preferably produced by (co) polymerizing an α-olefin in the presence of the olefin polymerization catalyst as described above.

  Specific embodiments for producing the octene (co) polymer (ii) will be described in detail below.

  In the present invention, the polymerization reaction is carried out in a hydrocarbon medium. Specific examples of such hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic carbons such as cyclopentane, cyclohexane, and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as hydrogen, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and petroleum fractions such as gasoline, kerosene and light oil. Furthermore, the olefin used for superposition | polymerization can also be used.

In the present invention, the polymerization is carried out in the presence of the olefin polymerization catalyst as described above. In this case, the Group IV transition metal compound (A) is usually used as the concentration of the transition metal atom in the polymerization reaction system. It is used in an amount ranging from 10 ⁻⁸ to 1 gram atom / liter, preferably from 10 ⁻⁷ to 10 ⁻¹ gram atom / liter.

  The (B-1) component has a molar ratio [(B-1) / M] of the component (B-1) and all transition metal atoms (M) in the component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (B-2) has a molar ratio [(B-2) / M] of (B-2) component to all transition metal atoms (M) in component (A) of usually 100 to 25000, preferably The amount used is 500 to 10,000. The component (B-3) has a molar ratio [(B-3) / M] of the aluminum atom in the component (B-3) and the total transition metal (M) in the component (A) of usually 10 to 10. The amount used is 5000, preferably 20-2000. In the component (B-4), the molar ratio [(B-4) / M] of the component (B-4) and the transition metal atom (M) in the component (A) is usually 1 to 50, preferably 1. It is used in such an amount that it becomes ˜20.

  Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-180 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

  The kinematic viscosity at 100 ° C. of the olefin polymer depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity is high, and if the molecular weight is low, the viscosity is low. Therefore, the kinematic viscosity at 100 ° C. is adjusted by adjusting the molecular weight. Moreover, the molecular weight distribution (Mw / Mn) of the polymer obtained can be adjusted to 1.8 or less by removing the low molecular weight component of the polymer obtained by a conventionally known method such as vacuum distillation. .

Moreover, in this invention, (iii) fatty acid ester whose kinematic viscosity in 100 degreeC is 20 mm < ² > / s or less is contained. When the kinematic viscosity is within this range, when adjusting the kinematic viscosity of the entire lubricating oil composition, it is possible to add an amount sufficient to suppress swelling of the lubricating oil sealant.

(Iii) Although it does not specifically limit as fatty acid ester whose kinematic viscosity in 100 degreeC is 20 mm < ² > / s or less, The following fatty acid ester which consists only of carbon, oxygen, and hydrogen is mentioned.

  Monoesters made from monobasic acids and alcohols; diesters made from dibasic acids and alcohols, or diols and monobasic acids or acid mixtures; diols, triols (eg trimethylolpropane), tetraols (eg Pentaerythritol), hexaol (for example, dipentaerythritol) and the like, and a polyol ester produced by reacting a monobasic acid or an acid mixture. Examples of these esters include tridecyl pelargonate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, trimethylolpropane triheptanoate, pentaerythritol tetraheptanoate and the like.

  Specifically, from the viewpoint of compatibility with the 1-decene (co) polymer or 1-octene (co) polymer selected in the present invention, the alcohol moiety constituting the ester is an alcohol having a hydroxyl group having two or more functional groups. The fatty acid moiety is preferably a fatty acid having 8 or more carbon atoms. However, fatty acids having a carbon number of 20 or less, which are industrially easily available, are superior in terms of production cost. The fatty acid constituting the ester may be one kind, and even two or more kinds of acid mixtures sufficiently exhibit the performance disclosed in the present invention. More specifically, trimethylolpropane lauric acid stearic acid mixed triester, diisodecyl adipate, and the like, which are saturated hydrocarbon components such as 1-decene (co) polymer and 1-octene (co) polymer And an antioxidant having a polar group, a corrosion inhibitor, an antiwear agent, a friction modifier, a pour point depressant, a rust inhibitor, and a defoaming agent, which will be described later, from the viewpoint of compatibility.

  The lubricating oil composition of the present invention comprises (i) decene (co) polymer, (ii) octene (co) polymer, and (iii) when the total of the esters is 100% by mass. ) 90 to 10% by weight of polymer, preferably 80 to 20% by weight, (ii) 5 to 85% by weight of octene (co) polymer and 5 to 15% by weight of ester (iii). In the amount of. When (i) decene (co) polymer, (ii) octene (co) polymer and (iii) ester are included in the above ranges, the lubricating oil composition has an excellent balance between shear stability and low temperature viscosity characteristics. A thing is obtained. Moreover, by containing 5 mass% or more of ester, favorable compatibility is obtained with respect to lubricating oil sealing materials such as resins and elastomers in various internal combustion engines and industrial machines. Specifically, swelling of the lubricating oil sealing material can be suppressed. From the viewpoint of oxidation stability or heat resistance, the amount of ester is preferably 15% by mass or less. However, the total of (i) to (iii) is 100% by mass.

  Further, one of the characteristics of the lubricating oil composition of the present invention is that it contains 5 ppm or more and 75 ppm or less of boron atoms. Here, 1 ppm means that 1 mg of boron is contained in 1 kg of the composition. It has been found by the present invention that the anti-micropitting performance is particularly improved by containing a specific concentration of boron in the lubricating oil composition. It has also been found that the performance of the extreme pressure agent described later that is optionally added to the lubricating oil composition can be sufficiently exhibited. In addition, the boron atom in a lubricating oil composition originates in the boron compound mentioned later. Further, the content of boron atoms in the lubricating oil composition is measured by ICP emission spectroscopic analysis as in Examples described later.

  For example, the following hypothesis can be considered as a mechanism for producing such an effect.

  The gear part in industrial machines, etc. has a metal contact due to the surface convex part of the friction surface breaking through the oil film of the lubricating oil under high load conditions (also called extreme pressure lubrication conditions), resulting in an increase in the friction surface temperature, Due to the strong shear, the oil film is detached or removed from the friction surface, the friction and wear increase, and eventually seizure may occur, which may make the lubrication impossible.

(Therefore, in the lubricating oil composition of the present invention, it is preferable that an extreme pressure agent, which will be described later, can be formed on the metal surface, which can form a reaction film having higher affinity with the metal, under this extreme pressure lubrication condition. It is speculated that the coating on the metal surface with this extreme pressure agent is effective for improving the durability against micro-pitting, that is, peeling of micro-pieces from the tooth surface due to repeated compressive stress that the gear part receives under high load conditions. )
However, as described later, until the extreme pressure agent reaches an extreme pressure lubrication condition that forms a film on the metal surface, the hydrocarbon or other organic components constituting the lubricating oil composition are heated and sheared to cause extreme pressure. Carbonization may occur before the lubrication condition, and a carbide film may be formed on the metal surface.

  It is believed that the boron-containing compound acts as a dispersant that interferes with the carbide or carbide precursor before the carbide coating is formed and prevents the carbide from adhering to the metal surface. Furthermore, since boron has an affinity for metals, it is presumed that it bears part of extreme pressure performance or wear resistance.

  In particular, it is considered that the boron-containing compound is greatly involved in the metal with respect to the micropitting that causes metal peeling in a microscopic region, and the micropitting resistance is exhibited at a boron atom content of 5 ppm or more in the lubricating oil composition. Considering the long-term operation of the engine, it is preferable to contain 20 ppm or more. However, since the boron-containing compound is very polar with respect to saturated hydrocarbons such as 1-decene (co) polymer and 1-octene (co) polymer which are main components of the lubricating oil composition in the present invention, From the viewpoint of compatibility, the boron atom content needs to be 75 ppm or less, preferably 50 ppm or less. If it exceeds this range, it is considered that the solution is agglomerated due to poor compatibility and inhibits the low temperature viscosity characteristics of the lubricating oil composition as an aggregate.

  The boron-containing compound contained may be an organic compound or an inorganic compound. Inorganic compounds include boronic acid, its anhydrides, oxides and halides. Organoboron compounds include boron amides and esters. Also included are boronated acylated amines, boronated dispersants, boronated epoxides and boronated fatty acid esters of glycerol.

Boron oxide; boron oxide hydrate; boron trioxide; boron trifluoride; boron tribromide; boron trichloride; boronic acid (ie alkyl-B (OH) ₂ or aryl- Boric acids such as B (OH) 2), boric acid (ie H ₃ BO ₃ ), tetraboric acid (ie H ₂ B4O ₇ ), metaboric acid (ie HBO ₂ ), boron anhydride, etc., and such boron Included are acid boron amides and various esters. Complexes of boron trihalides with ethers, organic acids, inorganic acids, or hydrocarbons can also be used. Examples of such complexes include boron trifluoride-triethyl ester, boron trifluoride-phosphate, boron trichloride-chloroacetic acid, boron tribromide-dioxane, and boron trifluoride methyl ethyl ether. .

  The boron-containing compound is desirably an organic compound from the viewpoint of compatibility with other components of the lubricating oil composition.

  Specific examples of boronic acid include methylboronic acid, phenyl-boronic acid, cyclohexylboronic acid, p-heptylphenylboronic acid, dodecylboronic acid and the like. Suitable boron-containing compounds include, for example, boron oxide such as boron oxide, boron oxide hydrate, and boron trioxide.

  Boric acid esters include boric acid and, for example, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, cyclopentanol, 1-octanol, 2-octanol, dodecanol, behenyl alcohol, oleyl alcohol, stearyl alcohol, benzyl Alcohol, 2-butylcyclohexanol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1,2-cyclohexanediol, 1,3-octanediol, glycerol, pentaerythritol Diethylene glycol, carbitol, cellosolve, triethylene glycol, tripropylene glycol, phenol, naphthol, p-butylphenol , O, p-diheptylphenol, n-cyclohexylphenol, 2,2-bis {p-hydroxyphenyl) -propane, polyisobutene (molecular weight 1,500) substituted phenol, ethylene chlorohydrin, o-chlorophenol , M-nitrophenol, 6-bromooctanol, 7-keto-decanol and the like mono-, di-, and tri-organic esters with alcohols or phenols. Lower alcohols, 1,2-glycols, and 1-3-glycols, that is, those having less than about 8 carbon atoms are useful in the preparation of boronic esters.

  Methods for preparing esters of boronic acid are known, such as the reaction of boron trichloride with 3 moles of alcohol or phenol, or the preparation of tri-organoborates by reaction of boron oxide with alcohol or phenol. It is done. Another method includes direct esterification of tetraboric acid with 3 moles of alcohol or phenol, and another method includes, for example, cyclic boron by direct esterification of boric acid and glycol. Examples include acid alkylene formation.

  In some embodiments, the boron-containing compound is a compound in which an oil-soluble ashless dispersant is borated.

  Ashless dispersants have basic nitrogen and / or at least one hydroxyl group in the molecule. Boronated ashless dispersants are obtained by reacting boron with basic nitrogen and / or hydroxyl groups in the ashless dispersant. Suitable dispersants include alkenyl succinimides, alkenyl succinates, alkenyl succinate amides, Mannich bases, hydrocarbyl polyamines, polymeric polyamines, and the like.

  The alkenyl succinimide is formed by conventional methods such as heating an alkenyl succinic anhydride, acid, acid / ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group. be able to. Alkenyl succinic anhydrides can be readily made by heating a mixture of olefin and maleic anhydride, for example to about 180-220 ° C. The olefin is a polymer or copolymer of lower monoolefins such as ethylene, propylene, 1-butene, isobutene, and the like, and mixtures thereof. Exemplary alkenyl group sources have a gel permeation chromatography (GPC) number average molecular weight of 10,000 or more, such as from about 500 to about 2,500, for example from about 800 to about 1,500. Polyisobutene. In some embodiments, the polyisobutylene has a molecular weight of about 700 to about 5,000. The ratio of polyisobutylene succinic anhydride to amine is about 1.4 to about 3, and in a further example about 1.8 to about 2.2.

  The lubricant composition in the present invention may contain one of the above boron-containing compounds, or may be used from a combination of two or more.

  The lubricating oil composition of the present invention preferably further contains one or more extreme pressure agents.

  The extreme pressure agent in the present application is a general term for components other than (i) to (iii) and having an effect of preventing seizure, and is not particularly limited, but is not limited to sulfides, sulfoxides, sulfones, thiophosphine. Sulfur-based extreme pressure agents such as citrates, thiocarbonates, sulfurized fats and oils, sulfurized olefins; Phosphoric acids such as phosphate esters, phosphites, phosphate ester amine salts, phosphite amines; chlorinated hydrocarbons Examples thereof include halogen compounds. Two or more of these compounds may be used in combination.

  However, before reaching the extreme pressure lubrication condition, hydrocarbons or other organic components constituting the lubricating oil composition are carbonized before the extreme pressure lubrication condition by heating and shearing to form a carbide film on the metal surface. there is a possibility. For this reason, when the extreme pressure agent is used alone, the carbide coating inhibits contact between the extreme pressure agent and the metal surface, and there is a possibility that a sufficient effect of the extreme pressure agent cannot be expected.

  As a method of adding the boron-containing compound to the lubricating oil composition, the boron-containing compound may be added alone, but the lubricating oil composition in the present invention is composed of 1-decene (co) polymer and 1-octene (co-polymer). ) Since the main component is a saturated hydrocarbon such as a polymer, it is better to add it in a state dissolved in a lubricating base oil such as mineral oil or 1-decene (co) polymer, so that the dispersibility of the boron-containing compound is improved. It is preferable from the viewpoint. In any method, the boron-containing compound may be blended so that the boron atom content in the lubricating oil composition is 5 ppm to 75 ppm.

  Specifically, among the so-called extreme pressure agent packages in which various components such as extreme pressure agent components are pre-mixed, select the extreme pressure agent package in which the boron-containing compound is already added in a dissolved state. A method of adding to the lubricating oil composition is more preferable.

  When a predetermined amount of a boron-containing compound is added as an extreme pressure agent package, the addition amount of the extreme pressure agent package is 2 to 5 with respect to (i) to (iii) 100% by mass in the lubricating oil composition of the present invention. It is preferable to select the extreme pressure agent package containing the boron-containing compound so as to be the mass%. The extreme pressure agent component is added to the extreme pressure agent package in consideration of the concentration that can be sufficiently dispersed in the lubricating oil composition. In some cases, sufficient effects cannot be expected. On the other hand, if it exceeds 5% by mass, the lubricating oil composition aggregates due to incompatibility with a saturated hydrocarbon component such as 1-decene (co) polymer and 1-octene (co) polymer, and the lubricating oil as an aggregate The low temperature viscosity characteristics of the composition may be impaired.

  Preferable extreme pressure agents (packages) include LUBRIZOL's Angolamol 98A, AFTON CHEMICAL's HITEC1532, etc. In particular, HITEC307 manufactured by AFTON CHEMICAL is preferably used from the viewpoint of the balance between boron-containing compounds and other components. it can.

  In addition, the lubricating oil composition of the present invention includes additives such as viscosity index improvers, antioxidants, corrosion inhibitors, antiwear agents, friction modifiers, pour point depressants, rust inhibitors, and antifoaming agents. It may be included.

  The following can be illustrated as an additive used for the lubricating oil composition of this invention, These can be used individually or in combination of 2 or more types.

  Detergent / dispersant: metal sulfonate, metal phenate, metal phosphonate, succinimide and the like can be exemplified, and usually used in the range of 0 to 15% by mass with respect to (i) to (iii) 100% by mass. .

  Antiwear agent: Inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, polytetrafluoroethylene and the like can be exemplified. An antiwear agent is used in the range of 0-3 mass% with respect to (i)-(iii) 100 mass% as needed.

  Antioxidant: Phenolic and amine compounds such as 2,6-di-tert-butyl-4-methylphenol are exemplified. An antioxidant is used in the range of 0-3 mass% with respect to (i)-(iii) 100 mass% as needed.

  Rust preventive agent: Compounds such as various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates. A rust preventive agent is used in the range of 0-3 mass% with respect to (i)-(iii) 100 mass% as needed.

  Antifoaming agent: Silicone compounds such as dimethylsiloxane and silica gel dispersion, alcohol compounds or ester compounds can be exemplified. An antifoamer is used in the range of 0-0.2 mass% with respect to (i)-(iii) 100 mass% as needed.

  In addition to the above additives, a demulsifier, a colorant, an oily agent (oiliness improver), and the like can be used as necessary.

Moreover, since the specific (ii) octene (co) polymer is combined with specific (i) decene (co) polymer, the lubricating oil composition of this invention is excellent in shear stability. Shear stability is evaluated by a KRL shear stability test in accordance with the method described in German Industrial Standard DIN 52350-6. Specifically, the lubricating oil composition is placed under shearing conditions (1450 rpm) at 60 ° C. for 20 hours, and the rate of decrease in kinematic viscosity at 40 ° C. after the test relative to the kinematic viscosity at 40 ° C. before the test is determined. It represents that it is excellent in shear stability, so that this value is small. The lubricating oil composition of the present invention, when adjusting the kinematic viscosity at 40 ° C. to 288 mm ² / s or more 352 mm ² / s or less, dynamic at 40 ° C. after KRL shear stability tests conforming to DIN 52350-6 measurement The viscosity reduction rate is usually less than 10%, preferably less than 5%. Incidentally, the kinematic viscosity at 40 ° C. is not more than 288 mm ² / s or more 352 mm ² / s, indicating that this lubricating oil composition is a viscosity grade (ISO 3448) VG 320. Moreover, it is used especially suitably for the gear for wind power generators that it is a viscosity grade.

  Thus, the lubricating oil composition of the present invention comprises a specific (i) decene (co) polymer, (ii) octene (co) polymer, (iii) ester, and boron atoms in a specific amount. Therefore, it is excellent in shear stability, low-temperature viscosity characteristics, and anti-micropitting resistance, and also in excellent balance between oxidation stability, heat resistance, and temperature-viscosity characteristics.

≪Usage≫
The lubricating oil composition of the present invention can be used as industrial lubricating oil (gear oil, hydraulic oil) and grease base oil. Further, as described above, the lubricating oil composition of the present invention is particularly suitably used as a lubricating oil for wind power generators because it is excellent in shear stability, low-temperature viscosity characteristics and anti-micropitting performance. In addition, when it is excellent in shear stability and anti-micropitting performance, it can be made maintenance-free when used for a gear for a wind power generator. Moreover, it is preferable from the viewpoint of energy conversion efficiency from wind power to electric power that it is excellent in low-temperature viscosity characteristics.

  The wind power generator gear of the present invention is lubricated with the above-described lubricating oil composition.

  1-4 has shown the example of the wind power generator which has the said gear for wind generators. The wind power generator includes a planetary gear (gear) type power transmission device, specifically, a rotor nose 1, a receiving opening 2, a roller bearing 3, a rotor carrier 4, an azimuth bearing 5, an outer race. 6, inner race 7, tow pin 8, drive stage 9, driven stage 10, generator 11, sun gear 12, hollow gear 13, hollow gear 14, power motor casing 15, planetary gear carrier 16, vibration damping device 17, And a fixed rail 18. The function and operation of each part are the same as those disclosed in JP 2000-337245 A.

  The lubricating oil composition of the present invention is suitably used for lubrication in the gear part (gear part).

  As described above, the present invention relates to the following (1) to (7).

(1) A lubricating oil composition comprising the following (i) to (iii), having a kinematic viscosity at 40 ° C. of 30 mm ² / s to 750 mm ² / s and containing boron atoms of 5 ppm to 75 ppm.
(I) The kinematic viscosity at 100 ° C. of 90 to 10% by mass is 45 mm ² / s or less, contains 60 mol% or more of structural units derived from 1-decene, and has an acid value of less than 0.1 mgKOH / g ( Co) polymer (ii) having a kinematic viscosity at 100 ° C. of 5 to 85% by mass of 35 mm ² / s to 1,500 mm ² / s, containing 90 mol% or more of structural units derived from 1-octene, and a gel (Co) polymer (iii) having a molecular weight distribution measured by permeation chromatography of 1.8 or less (Co) 5 to 15% by mass of a fatty acid ester having a kinematic viscosity at 100 ° C. of 20 mm ² / s or less (provided that ( (The sum of i) to (iii) is 100% by mass.)
The lubricating oil composition is excellent in shear stability, low-temperature viscosity characteristics, and temperature-viscosity characteristics because a specific (ii) octene (co) polymer is combined with a specific (i) decene (co) polymer. Further, since the boron content is in a specific range, the micropitting resistance and low temperature viscosity characteristics are excellent.

  (2) The lubricating oil composition according to (1), further comprising one or more extreme pressure agents.

(3) The lubricating oil composition according to (1) or (2), wherein the lubricating oil composition has a kinematic viscosity at 40 ° C. of 190 mm ² / s to 750 mm ² / s.

When the kinematic viscosity at 40 ° C. is 750 mm ² / s or less, the fuel saving performance and the energy conversion efficiency are excellent. Moreover, when it is 190 mm < ² > / s or more, favorable lubricity and shear stability are shown as gear oil in a high temperature and / or high load state.

(4) kinematic viscosity at 40 ° C. of the lubricating oil composition is not more than 288 mm ² / s or more 352 mm ² / s, lowering kinematic viscosity at 40 ° C. after KRL shear stability tests conforming to DIN 52350-6 measurement The lubricating oil composition according to any one of (1) to (3), wherein the rate is less than 10%.

  Thus, when it is excellent in shear stability, it is used especially suitably for the gear for wind power generators.

(5) (ii) The lubricating oil composition according to any one of (1) to (4), wherein the octene (co) polymer has a kinematic viscosity at 100 ° C. of 150 mm ² / s to 1,200 mm ² / s. .

When the kinematic viscosity at 100 ° C. is 150 mm ² / s or more, excellent low-temperature viscosity characteristics are exhibited. Moreover, if it is 1200 mm < ² > / s or less, shear stability will be more excellent.

(6) (i) Lubricating oil composition in any one of (1)-(5) whose kinematic viscosity in 100 degreeC of a decene (co) polymer is 11 mm < ² > / s or less.

When the kinematic viscosity at 100 ° C. is 11 mm ² / s or less, the low temperature viscosity characteristics of the lubricating oil composition are more excellent.

  (7) A wind power generator gear lubricated with the lubricating oil composition according to any one of (1) to (6).

  Such a wind power generator gear can be maintenance-free and has excellent energy conversion efficiency from wind power to electric power.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.

<Average molecular weight and molecular weight distribution>
The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured as follows using GPC (Chromatopack C-R4A) manufactured by Shimadzu Corporation. As separation columns, TSKG6000H XL, G4000H XL, G3000H XL, G2000H XL were used, the column temperature was 40 ° C., the mobile phase was tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), the development rate was 0.8 ml / min, The sample concentration was 0.2 mass%, the sample injection amount was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used.

<Viscosity characteristics>
The kinematic viscosity at 100 ° C. and 40 ° C. and the viscosity index were measured and calculated by the method described in JIS K2283.

<Shear stability>
The shear stability of the lubricating oil composition was evaluated using a KRL shear stability tester in accordance with the method described in DIN 52350-6. The blended oil was placed under shearing conditions (1450 rpm) at 60 ° C. for 20 hours, and the rate of decrease in kinematic viscosity at 40 ° C. before and after the test was evaluated.

  After applying shear stress by the above method, good durability is exhibited if the rate of decrease in kinematic viscosity is less than 10%. When the rate of decrease in kinematic viscosity is less than 5%, extremely excellent durability is exhibited.

<-30 ° C viscosity>
The −30 ° C. viscosity was measured with a Brookfield viscometer in accordance with ASTM D2983. In consideration of measurement errors, the -30 ° C viscosity was classified into the following three stages.

High: More than 100,000 mPa · s Medium: More than 80,000 to 100,000 mPa · s
Low: 80,000 mPa · s or less If the viscosity at −30 ° C. is 100,000 mPa · s or less, good lubricity can be maintained at extremely low temperatures up to about −40 ° C., and excellent fuel economy and energy Indicates conversion efficiency. In particular, when it is 80,000 mPa · s or less, excellent fuel economy and energy conversion efficiency are exhibited. If it exceeds 100,000 mPa · s at −30 ° C., fuel economy and energy conversion efficiency in a cryogenic environment are poor.

<Micropitting failure loading stage>
The failed load stage was measured by the FVA-54 / 7 micropitting test specified by the Drive Technology Research Federation (FVA). If the reject load stage is 10 or more, excellent micropitting resistance is exhibited.

<(I) (Co) polymer comprising 1-decene>
(I) Kinematic viscosity at 100 ° C. is 45 mm ² / s or less, and as a decene (co) polymer comprising 1-decene, poly-α-olefin (PAO) manufactured by NESTE OIL, NEXBASE 2006 (kinetic at 100 ° C. Viscosity, 6 mm ² / s) was used. The acid value measured according to JIS K2501 was less than 0.1 mgKOH / g.

<(Ii) (Co) polymer having 1-octene as monomer>
(Ii) An octene (co) polymer having 1-octene as a monomer was produced by the following polymerization example.

  The (methyl) (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride used in the polymerization examples was synthesized by the following method.

[Synthesis of 6,6′-methyl (p-tolyl) fulvene]
Under a nitrogen atmosphere, 5.9 g (81.9 mmol) of lithium cyclopentadiene was added to a 200 ml three-necked flask, and 100 ml of dehydrated diethyl ether was further added and stirred. The slurry solution was cooled in an ice bath, and 10.0 g (74.5 mmol) of 4′-methylacetophenone was added dropwise. The mixture was then stirred at room temperature for 20 hours, and the resulting solution was quenched with dilute aqueous hydrochloric acid. 50 ml of hexane was added, and the organic layer was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting viscous liquid was separated by column chromatography with hexane to obtain the desired product as a red viscous liquid (yield 9.8 g, yield 72%).

[Synthesis of (methyl) (p-tolyl) cyclopentadienyl (octamethyloctahydrodibenzofluorenyl) methane]
Under a nitrogen atmosphere, 80 ml of tetrahydrofuran and 5.0 g (12.9 mmol) of octamethyloctahydrodibenzofluorene were mixed in a 200 ml three-necked flask. The solution was cooled to −20 ° C. and then 8.45 ml of n-butyllithium ( 1.61 M hexane solution, 13.5 mmol) was slowly added dropwise and stirred at room temperature for 5 hours. Thereafter, the reaction solution was cooled to −20 ° C., and 2.6 g (14.2 mmol) of 6,6′-methyl (p-tolyl) fulvene was slowly added dropwise, followed by stirring for 1 hour while gradually returning to room temperature. The reaction was quenched with dilute aqueous hydrochloric acid and extracted with diethyl ether. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the obtained solid was recrystallized from methanol to obtain the desired product as a white solid (yield 7.2 g, yield 98%).

<(Iii) Esters>
(Iii) Diisodecyl adipate (DIDA) manufactured by Daihachi Chemical Co., Ltd., which is a fatty acid ester, was used as an ester having a kinematic viscosity at 100 ° C. of 20 mm ² / s or less.

<Extreme pressure agent package>
Extreme pressure agent A: A commercially available extreme pressure agent package (HITEC 307 manufactured by AFTON CHEMICAL) was used as an extreme pressure agent package having a boron content of 1,260 ppm.

  Extreme pressure agent B: A commercially available extreme pressure agent package (HITEC 343 manufactured by AFTON CHEMICAL) was used as an extreme pressure agent package having a boron content of less than 10 ppm.

  The boron content in the extreme pressure agent package was measured by ICP emission spectroscopy. The boron content in the lubricating oil composition was determined by conversion from the boron content in the extreme pressure agent package and the blending amount of each component.

[Polymerization Example 1]
1000 ml of 1-octene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature inside the system was raised to 65 ° C., and hydrogen was supplied to adjust the total pressure to 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.0007 mmol of heptane solution of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and hexane solution of methylaluminoxane (MMAO-3A : Manufactured by Tosoh Finechem Co., Ltd.), 0.35 mmol of Al concentration was injected with nitrogen, polymerization was performed at 70 ° C. for 60 minutes with a stirring rotation speed of 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. After depressurization, n-heptane was added to the taken-out solution, transferred to a separatory funnel, added to 100 ml of 1N hydrochloric acid, shaken, allowed to stand for about 10 minutes, and then separated into oil and water. After separating the organic layer, the organic layer was washed with water, a small amount of sodium sulfate was added to the organic layer, and the mixture was allowed to stand for about 10 minutes for dehydration. Then, after filtering and removing sodium sulfate, n-heptane and unreacted 1-octene were distilled off at 135 ° C. under reduced pressure (300 mmHg). The obtained transparent liquid polymer (1-octene polymer) was 83.7 g.

The obtained transparent liquid 1-octene polymer (Polymer 1) had a molecular weight (Mn) of 6,450 measured by gel permeation chromatography and a dispersion (Mw / Mn) of 1.67. The kinematic viscosity measured by the method described in JIS K2283 was 300 mm ² / s at 100 ° C. and 3,750 mm ² / s at 40 ° C., and the viscosity index calculated from these kinematic viscosities was 227.

[Polymerization Example 2]
1000 ml of 1-octene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature in the system was raised to 45 ° C., and hydrogen was supplied to make the total pressure 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.001 mmol of a heptane solution of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and a hexane solution of methylaluminoxane (MMAO-3A : Manufactured by Tosoh Finechem Co., Ltd.), 0.50 mmol of Al concentration was injected with nitrogen, and the polymerization was carried out at 50 ° C. for 60 minutes at a stirring rotation speed of 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. After depressurization, n-heptane was added to the taken-out solution, transferred to a separatory funnel, added to 100 ml of 1N hydrochloric acid, shaken, allowed to stand for about 10 minutes, and then separated into oil and water. After separating the organic layer, the organic layer was washed with water, a small amount of sodium sulfate was added to the organic layer, and the mixture was allowed to stand for about 10 minutes for dehydration. Then, after filtering and removing sodium sulfate, n-heptane and unreacted 1-octene were distilled off at 135 ° C. under reduced pressure (300 mmHg). The obtained transparent liquid polymer (1-octene polymer) was 107.6 g.

The obtained transparent liquid 1-octene polymer (polymer 2) had a molecular weight (Mn) of 9,940 as measured by gel permeation chromatography and a dispersion (Mw / Mn) of 1.64. Further, the kinematic viscosity measured by the method described in JIS K2283, was 9,604mm ² / s at 640mm ² / s, 40 ℃ at 100 ° C., a viscosity index calculated from these kinematic viscosity was 253.

[Polymerization Example 3]
1000 ml of 1-octene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature in the system was raised to 35 ° C., and hydrogen was supplied to adjust the total pressure to 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.001 mmol of a heptane solution of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and a hexane solution of methylaluminoxane (MMAO-3A : Manufactured by Tosoh Finechem Co., Ltd.), 0.50 mmol of Al concentration was press-fitted with nitrogen, and the polymerization was carried out at 40 ° C. for 60 minutes at a stirring rotation speed of 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. After depressurization, n-heptane was added to the taken-out solution, transferred to a separatory funnel, added to 100 ml of 1N hydrochloric acid, shaken, allowed to stand for about 10 minutes, and then separated into oil and water. After separating the organic layer, the organic layer was washed with water, a small amount of sodium sulfate was added to the organic layer, and the mixture was allowed to stand for about 10 minutes for dehydration. Then, after filtering and removing sodium sulfate, n-heptane and unreacted 1-octene were distilled off at 135 ° C. under reduced pressure (300 mmHg). The obtained transparent liquid polymer (1-octene polymer) was 108.8 g.

The obtained transparent liquid 1-octene polymer (polymer 3) had a molecular weight (Mn) of 11,430 as measured by gel permeation chromatography and a dispersion (Mw / Mn) of 1.66. Further, the kinematic viscosity measured by the method described in JIS K2283, a 14,720mm ² / s at 920mm ² / s, 40 ℃ at 100 ° C., a viscosity index calculated from these kinematic viscosity was 269.

[Polymerization Example 4]
A stainless steel autoclave with an internal volume of 2 L that has been sufficiently purged with nitrogen is charged with 300 ml of n-heptane and 700 ml of 1-hexene, the temperature inside the system is raised to 75 ° C., and hydrogen is supplied to bring the total pressure to 3 MPa. -G. Next, 0.4 mmol of triisobutylaluminum, 0.0015 mmol of heptane solution of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and hexane solution of methylaluminoxane (MMAO-3A : Tosoh Finechem Co., Ltd.) was polymerized at 80 ° C. for 60 minutes by press-fitting 0.75 mmol of Al with nitrogen with stirring at 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. After depressurization, n-heptane was added to the taken-out solution, transferred to a separatory funnel, added to 100 ml of 1N hydrochloric acid, shaken, allowed to stand for about 10 minutes, and then separated into oil and water. After separating the organic layer, the organic layer was washed with water, a small amount of sodium sulfate was added to the organic layer, and the mixture was allowed to stand for about 10 minutes for dehydration. Then, after filtering and removing sodium sulfate, n-heptane and unreacted 1-hexene were distilled off at 135 ° C. under reduced pressure (300 mmHg). The obtained transparent liquid polymer (1-hexene polymer) was 333.0 g.

The obtained transparent liquid 1-hexene polymer (polymer 4) had a molecular weight (Mn) of 3,900 as measured by gel permeation chromatography and a dispersion (Mw / Mn) of 1.73. Further, the kinematic viscosity measured by the method described in JIS K2283, was 6,296mm ² / s at 319mm ² / s, 40 ℃ at 100 ° C., a viscosity index calculated from these kinematic viscosity was 190.

[Example 1]
The (co) polymer comprising 1-decene is 33.2% by mass, the (co) polymer having 1-octene as a monomer, 56.5% by mass of polymer 1 obtained in Polymerization Example 1 and ester. 10.3 mass% and 2.7 mass% of extreme pressure agent A were mix | blended, and mixing | blending adjustment was performed so that 40 degreeC kinematic viscosity might be 288-352 mm < ² > / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 1.

[Example 2]
The (co) polymer comprising 1-decene is 45.5% by mass, the (co) polymer having 1-octene as a monomer, the polymer 2 obtained in Polymerization Example 2 is 44.2% by mass, and the ester is 10.3 mass% and 2.7 mass% of extreme pressure agent A were mix | blended, and mixing | blending adjustment was performed so that 40 degreeC kinematic viscosity might be 288-352 mm < ² > / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 1.

[Example 3]
As a (co) polymer containing 19.7-decene (co) polymer and 1-octene as a monomer, 40.0% by mass of polymer 3 obtained in Polymerization Example 3 and ester 10.3 mass% and 2.7 mass% of extreme pressure agent A were mix | blended, and mixing | blending adjustment was performed so that 40 degreeC kinematic viscosity might be 288-352 mm < ² > / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 1.

[Example 4]
As a (co) polymer comprising 1-decene (co) polymer 45.4% by mass and 1-octene as a monomer, 44.2% by mass of polymer 2 obtained in polymerization example 2 and ester 10.4 mass%, extreme pressure agent A 3.5 mass% was mix | blended, and mixing | blending adjustment was performed so that 40 degreeC kinematic viscosity might be 288-352 mm < ² > / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 1.

[Comparative Example 1]
As a (co) polymer having 1-decene (co) polymer of 32.3% by mass and 1-octene as a monomer, 57.1% by mass of polymer 1 obtained in Polymerization Example 1 and an ester 10.6 mass% and 6.0 mass% of extreme pressure agent A were mix | blended, and mixing | blending adjustment was performed so that 40 degreeC kinematic viscosity might be 288-352 mm < ² > / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 2.

[Comparative Example 2]
As a polymer having 1-decene (co) polymer as 23.6% by mass and 1-decene as a monomer, ExxonMobil Chemical's Spectrasyn Ultra-150 is 66.1% by mass, and ester is 10.3% by mass. , 2.7 mass% of extreme pressure agent A was blended, and blending adjustment was performed so that the 40 ° C. kinematic viscosity was 288 to 352 mm ² / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 2.

[Comparative Example 3]
As a polymer having 1-decene (co) polymer 34.0% by mass, 1-decene as a monomer, ExxonMobil Chemical's Spectrasyn Ultra-300 is 55.7% by mass, and ester is 10.3% by mass. The mixture was adjusted so that the extreme pressure agent A was 2.7% by mass and the kinematic viscosity at 40 ° C. was 288 to 352 mm ² / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 2.

[Comparative Example 4]
As a polymer having 1-decene (co) polymer as 51.2% by mass and 1-decene as a monomer, ExxonMobil Chemical's Spectrasyn Ultra-1000 is 38.5% by mass, and ester is 10.3% by mass. , 2.7 mass% of extreme pressure agent A was blended, and blending adjustment was performed so that the 40 ° C. kinematic viscosity was 288 to 352 mm ² / s. The lubricating properties of the resulting lubricating oil composition are shown in Table 2.

[Comparative Example 5]
Example 1 was followed except that the extreme pressure agent A in Example 1 was changed to the extreme pressure agent B. The lubricating properties of the resulting lubricating oil composition are shown in Table 2.

  Polymerization Examples 1 to 3 are superior in viscosity index, that is, temperature-viscosity characteristics, as compared with the polymer having 6 carbon atoms, that is, 1-hexene as a monomer shown in Polymerization Example 4. Therefore, it is clear that the low temperature viscosity characteristic of the lubricating oil composition in the present invention is superior to the lubricating oil composition blended with a polymer containing 1-hexene as a monomer.

  Examples 1-4 (Table 1) are excellent in -30 degreeC viscosity compared with the comparative example 1 (Table 2) whose boron content exceeds 75 ppm.

  Moreover, Examples 1-4 (Table 1) are excellent in shear stability compared with Comparative Examples 2-4 (Table 2) in which the polymer which uses 1-decene as a monomer is contained in the lubricating oil composition. .

  Moreover, Examples 1-4 (Table 1) are excellent in micropitting-proof performance compared with the comparative example 5 (Table 2) with low boron content.

1: rotor nose 2: accommodation opening 3: roller bearing 4: rotor carrier 5: azimuth bearing 8: tow pin 9: drive stage 10: driven stage 11: generator 12: solar gear 13: hollow gear 14: hollow Gear 15: Power motor casing 16: Planetary gear carrier 17: Vibration damper 18: Fixed rail

Claims (7)

A lubricating oil composition comprising the following (i) to (iii), having a kinematic viscosity at 40 ° C. of 30 mm ² / s to 750 mm ² / s and containing boron atoms of 5 ppm to 75 ppm.
(I) The kinematic viscosity at 100 ° C. of 90 to 10% by mass is 45 mm ² / s or less, 60 mol% or more of the structural unit is composed of 1-decene, and the acid value is less than 0.1 mgKOH / g (both ) Polymer (ii) The kinematic viscosity at 100 ° C. of 5 to 85% by mass is 35 mm ² / s or more and 1,500 mm ² / s or less, 90 mol% or more of the structural unit is composed of 1-octene, and gel permeation (Co) polymer (iii) whose molecular weight distribution measured by chromatography is 1.8 or less Fatty acid ester having a kinematic viscosity at 100 ° C. of 5 to 15% by mass of 20 mm ² / s or less (provided that (i) (The sum of (iii) is 100% by mass.)   The lubricating oil composition according to claim 1, further comprising one or more extreme pressure agents. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a kinematic viscosity at 40 ° C. of 190 mm ² / s or more and 750 mm ² / s or less. Kinematic viscosity at 40 ° C. of the lubricating oil composition is not more than 288 mm ² / s or more 352 mm ² / s, kinematic viscosity reduction rate at 40 ° C. after KRL shear stability tests conforming to DIN 52350-6 measurement 10% The lubricating oil composition according to any one of claims 1 to 3, wherein the lubricating oil composition is less than 1. The lubricating oil according to any one of claims 1 to 4, wherein the (co) polymer of (ii) has a kinematic viscosity at 100 ° C of 150 mm ² / s to 1,200 mm ² / s. Composition. 6. The lubricating oil composition according to claim 1, wherein the (i) 1-decene (co) polymer has a kinematic viscosity at 100 ° C. of 11 mm ² / s or less. object.   The gear for wind power generators with which the lubricating oil composition of any one of Claims 1-6 is filled.

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